Polyarylene sulfide resin composition and formed article

ABSTRACT

The present invention relates to a polyarylene sulfide resin composition having good processability and showing excellent properties due to its more improved miscibility with other polymer materials or fillers, and a formed article. Such polyarylene sulfide resin composition includes a polyarylene sulfide including a disulfide repeating unit in the repeating units of the main chain; and at least one component selected from the group consisting of a thermoplastic resin, a thermoplastic elastomer, and a filler.

TECHNICAL FIELD

The present invention relates to a polyarylene sulfide resin compositionshowing excellent properties because of more improved compatibility withother polymer materials or fillers, and a formed article.

BACKGROUND OF THE INVENTION

Now, polyarylene sulfide is a representative engineering plastic, andthe demand for the products being used in a high temperature andcorrosive environment or the electronic goods is increasing due to itshigh heat resistance and chemical resistance, flame resistance, electricinsulation, and so on.

Among the polyarylene sulfides, polyphenylene sulfide (PPS) is one andonly commercially on sale now. The commercial preparation process of PPSbeing applicable until now is the method of carrying out a solutionpolymerization of p-dichlorobenzene (pDCB) and sodium sulfide in a polarorganic solvent such as N-methylpyrrolidone. The method is known asMacallum process.

However, when the polyarylene sulfide is prepared by the Macallumprocess of such solution polymerization type, a salt type by-product maybe formed in a solution polymerization process using sodium sulfide, andthus there is a disadvantage of requiring a washing or drying processfor eliminating a salt type by-product or a residual organic solvent.Furthermore, since the polyarylene sulfide prepared by such Macallumprocess has a powder form, the post processability and workability maydecrease. Moreover, in the case of the polyarylene sulfide prepared bythe Macallum process, the polyarylene sulfide includes a considerableamount of oligomer type polymer chains having low molecular weight, andthus there is a problem of that the processability decreases because aconsiderable amount of flash occurred when forming an article requiringhigh degree of precision and a separate process was required foreliminating the same.

Accordingly, a method of melt-polymerizing a reactant includingdiiodoaromatic compounds and sulfur element was suggested as the methodof preparing the polyarylene sulfide such as PPS and the like. Suchmethod does not form a salt type by-product and not use an organicsolvent in the preparation process of the polyarylene sulfide, and thusit does not require an additional process for eliminating them.Furthermore, since the polyarylene sulfide prepared finally has a pelletform, there is an advantage of easy post processability and goodworkability.

However, in the case of the polyarylene sulfide prepared by themelt-polymerization method, the ends of the main chain were composed ofiodine and most aryl groups (representatively, benzene). Therefore,there was a disadvantage of that such polyarylene sulfide was inferiorin the compatibility with other polymer materials or all sorts ofreinforcements or fillers like glass fiber and the like due to thecharacteristics of its main chain structure.

Due to this, it was hard to compound the polyarylene sulfide prepared bythe melt-polymerization method with other polymer materials or fillersfor securing optimized properties suitable to various uses, and it wasdifficult to show optimized properties even if it was compounded withthem. Due to such problem, in the case of prior known polyarylenesulfide resin composition, it was true that it was difficult to exhibitsufficient properties suitable for the use and the applications forvarious uses were limited.

And, it has been continuously required to develop a polyarylene sulfideshowing reduced flash occurrence and more excellent processability whenit is intended to prepare an article requiring high degree of precision.

SUMMARY OF THE INVENTION

It is an aspect of the present invention to provide a polyarylenesulfide resin composition showing good processability and excellentproperties because of its more improved miscibility with other polymermaterials or fillers.

It is another aspect of the present invention to provide a formedarticle including the polyarylene sulfide resin composition and showingthe optimized properties for its use, and a preparation method thereof.

The present invention provides a polyarylene sulfide resin composition,including a polyarylene sulfide including a disulfide repeating unit inthe repeating units of the main chain; and at least one componentselected from the group consisting of a thermoplastic resin, athermoplastic elastomer, and a filler.

The present invention also provides a method of preparing a formedarticle, including the step of extruding said polyarylene sulfide resincomposition.

The present invention also provides a formed article including saidpolyarylene sulfide resin composition.

Hereinafter, the polyarylene sulfide resin composition according tospecific embodiment of the invention, the formed article including thesame, and the preparation method thereof are explained in more detail.However, the embodiment is provided only for an example of theinvention, and the scope of the invention is not limited to or by themand it is obvious to a person skilled in the art that variousmodifications are possible in the scope of the invention.

In this description, “include” or “comprise” means to include anycomponents (or ingredients) without particular limitation unless thereis no particular mention about them, and it cannot be interpreted as ameaning of excluding an addition of other components (or ingredients).

According to one embodiment of the invention, a polyarylene sulfideresin composition, including a polyarylene sulfide including a disulfiderepeating unit in the repeating units of the main chain; and at leastone component selected from the group consisting of a thermoplasticresin, a thermoplastic elastomer, and a filler is provided.

In such polyarylene sulfide resin composition, the disulfide repeatingunit may mean the polyarylene disulfide repeating unit of GeneralFormula 2 including the disulfide bond (—S—S— linkage) instead of thesulfide bond in the repeating unit of general polyarylene sulfiderepresented by General Formula 1:

in General Formulae 1 and 2, Ar represents a substituted ornon-substituted arylene group.

Like this, as the polyarylene sulfide included in the resin compositionof one embodiment has the disulfide repeating unit, it is possible toprevent the oligomer type polymer chain having excessively low molecularweight from being included in the polyarylene sulfide. It seems becausethe disulfide bond in the disulfide repeating unit continuously causes asulfur transfer reaction between the polymer chains of the polyarylenesulfide, and can uniformize the molecular weight of the polymer chainsof the polyarylene sulfide on the whole. As the result, the polyarylenesulfide included in the resin composition of one embodiment can includethe oligomer type polymer chains having excessively low molecular weightminimally, and can show relatively narrow and symmetric molecular weightdistribution curve close to a normal distribution, because the molecularweight distribution of the whole polymer chains is uniformized.Therefore, the resin composition of one embodiment including thepolyarylene sulfide can show reduced flash occurrence and more improvedprocessability even when it is used for preparing an article requiringhigh degree of precision.

And, the disulfide repeating unit may be included in the amount of about3 weight % or less, about 0.01 to 3.0 weight %, or about 0.1 to 2.0weight %, based on the whole polyarylene sulfide. According to this, theprocessability improvement effect of the disulfide repeating unit may beoptimized, and it is possible to prevent the properties of thepolyarylene sulfide from getting worse because of the excessively muchdisulfide repeating unit.

And, though it will be explained in more detail later, in the resincomposition of one embodiment, the polyarylene sulfide may be what isprepared by adding a polymerization inhibitor step by step, morespecifically, the polyarylene sulfide may be what is prepared bymelt-polymerizing a reactant including diiodoaromatic compounds andsulfur element while adding the polymerization inhibitor step by step,dividedly into 2 times or more.

The present inventors revealed that a polyarylene sulfide which showedbetter compatibility with other polymer materials or fillers and couldbe compounded with various materials and could realize optimizedproperties suitable to various uses could be obtained by adding thepolymerization inhibitor step by step, in the process of preparing apolyarylene sulfide by melt-polymerizing a reactant including adiiodoaromatic compound and sulfur element.

It seems to be caused by the theoretical principal disclosed below.

When the polymerization inhibitor is added in the process of themelt-polymerization, iodomolecules are formed at the ends of the polymerchains. At this time, the reactivity of iodine formed at the end of thepolymer chain can be increased because the final step of the reactionwhere the polymerization inhibitor is added is carried out at hightemperature of around 300° C. Therefore, such iodine can cause thegeneration of branched structure or crosslinked bond of the polymerchain, and, if the polymerization inhibitor is added thereto step bystep, the formed iodine may be eliminated more effectively than thepolymerization inhibitor is added at a time and the generation of thebranched structure or the crosslinked bond can be suppressed more. Asthe result, the linearity of the polyarylene sulfide polymer chain canbe improved and thus it is possible to obtain the polyarylene sulfidewhich shows better compatibility with other polymer materials or fillersand can be compounded with various materials and can realize optimizedproperties suitable to various uses.

Meanwhile, in the resin composition of one embodiment, the polyarylenesulfide may include carboxyl group (—COOH) or amine group (—NH₂) bondedto at least part of end groups of the main chain.

From the result of continuous research of the present inventors, it wasrevealed that a polyarylene sulfide which showed better compatibilitywith other polymer materials or fillers and could be compounded withvarious materials and could realize optimized properties suitable tovarious uses could be obtained by introducing the specific end groups,in the process of preparing a polyarylene sulfide by melt-polymerizing areactant including a diiodoaromatic compound and sulfur element.

Namely, in the case of the polyarylene sulfide prepared by priormelt-polymerization method, the ends of the main chain were composed ofiodine and most aryl groups (representatively, benzene). Therefore,there was a disadvantage of that such polyarylene sulfide was inferiorin the compatibility with other polymer materials or all sorts ofreinforcements or fillers like glass fiber and the like due to thecharacteristics of its main chain structure.

However, in the case of the polyarylene sulfide including a reactivegroup such as carboxyl group (—COOH) or amine group (—NH₂) bonded to atleast part of end groups of the main chain, it is recognized that itshows excellent compatibility with other polymer materials or fillersbecause of the existence of the reactive group. As the result, in thecase of the resin composition including other polymer materials such asa thermoplastic resin or a thermoplastic elastomer or a filler incompany with the polyarylene sulfide, it shows optimized propertyincrease caused by mixing (for example, compounding) with othermaterials while having good heat resistance and chemical resistanceunique to the polyarylene sulfide and excellent mechanical properties,and thus it makes it possible to provide a formed article havingexcellent properties suitable to various uses. Therefore, polyarylenesulfide resin compositions can be applied to various uses by virtue ofthe resin composition of one embodiment.

Finally, the resin composition of one embodiment hardly generatesflashes and shows excellent processability when forming an articlerequiring high degree of precision, and can show more excellentsynergistic effect of compounding because of good compatibility of thepolyarylene sulfide and other materials, and thus makes it possible toprovide a formed article having the properties suitable to various uses.

The polyarylene sulfide included in the resin composition of oneembodiment may show the peak of about 1600 to 1800 cm⁻¹ derived fromcarboxyl groups of the ends of the main chain or the peak of about 3300to 3500 cm⁻¹ derived from amine group, in a FT-IR spectrum, when it isanalyzed with FT-IR spectroscopy. At this time, the intensity of thepeak of 1600 to 1800 cm⁻¹ or the peak of 3300 to 3500 cm⁻¹ maycorrespond to the amount of carboxyl groups or amine groups connected tothe ends of main chain.

According to one example, in the FT-IR spectrum of the polyarylenesulfide of one embodiment, if the height of the ring stretch peak shownat about 1400 to 1600 cm⁻¹ is assumed as the intensity of 100%, therelative height intensity of the peak of about 1600 to 1800 cm⁻¹ orabout 3300 to 3500 cm⁻¹ may be about 0.001 to 10%, about 0.01 to 7%,about 0.1 to 4%, or about 0.5 to 3.5%. At this time, the ring stretchpeak shown at 1400 to 1600 cm⁻¹ may be what is derived from the arylenegroup such as phenylene and the like included in the main chain of thepolyarylene sulfide. Since the height intensity of the peak of about1600 to 1800 cm⁻¹ derived from carboxyl groups or the peak of about 3300to 3500 cm⁻¹ derived from amine groups is about 0.001 to 10%, about 0.01to 7%, about 0.1 to 4%, or about 0.5 to 3.5% in comparison to the heightintensity of the peak derived from the arylene group (for example,phenylene group), the polyarylene sulfide included in the resincomposition of one embodiment can show good compatibility with otherpolymer materials or fillers and can maintain excellent propertiesunique to the polyarylene sulfide. Therefore, the resin composition ofone embodiment can exhibit more excellent synergistic effect accordingto the compounding of the polyarylene sulfide and other polymermaterials or fillers.

Meanwhile, the melting temperature of the polyarylene sulfide includedin the resin composition of one embodiment may be about 265 to 290° C.,about 270 to 285° C., or about 275 to 283° C. Because of such meltingtemperature range, the polyarylene sulfide of one embodiment obtained bymelt-polymerization method, to which carboxyl group or amine group isintroduced, can show excellent heat resistance and flame retardance.

And, the number average molecular weight of the polyarylene sulfide maybe about 5,000 to 50,000, about 8,000 to 40,000, or about 10,000 to30,000. The polydispersity index defined as the weight average molecularweight divided by the number average molecular weight may be about 2.0to 4.5, about 2.0 to 4.0, or about 2.0 to 3.5. Because the polyarylenesulfide of one embodiment has such polydispersity index and molecularweight range, it can show excellent mechanical properties andprocessability and can be processed into various formed articles forvarious uses.

Furthermore, above polyarylene sulfide of one embodiment may have themelt viscosity of about 10 to 50,000 poise, about 100 to 20,000, orabout 300 to 10,000, which is measured with a rotational viscometer at300° C. The polyarylene sulfide having such melt viscosity and the resincomposition of one embodiment including the same can show superiormechanical properties in company with excellent processability.

For example, the polyarylene sulfide included in the resin compositionof one embodiment may have the tensile strength of about 100 to 900kgf/cm², about 200 to 800 kgf/cm², or about 300 to 700 kgf/cm², which ismeasured according to ASTM D 638, and the elongation of about 1 to 10%,about 1 to 8%, or about 1 to 6%, which is measured according to ASTM D638. Furthermore, the polyarylene sulfide of one embodiment may have theflexural strength of about 100 to 2,000 kgf/cm², about 500 to 2,000kgf/cm², or about 1,000 to 2,000 kgf/cm², which is measured according toASTM D 790, and the impact strength of about 1 to 100 J/m, about 5 to 50J/m, or about 10 to 20 J/m, which is measured according to ASTM D 256.Like this, the polyarylene sulfide of one embodiment can show goodcompatibility with other polymer materials or fillers and can exhibitexcellent properties. In company with this, the resin composition of oneembodiment can exhibit higher synergistic effect caused by thecompounding of each component and excellent properties suitable tovarious uses because it can show excellent compatibility with otherpolymer materials and fillers disclosed above.

Meanwhile, the resin composition of one embodiment includes otherpolymer material such as a thermoplastic resin or a thermoplasticelastomer or a filler in company with the polyarylene sulfide includingcarboxyl group or amine group bonded to the ends of the main chain. Atthis time, as the example of polymer material which can be included inthe resin composition of one embodiment, there may be variousthermoplastic resins such as polyvinylalcohol-based resins,vinylchloride-based resins, polyamide-based resins, polyolefin-basedresins, polyester-based resins, and the like; or various thermoplasticelastomers such as polyvinylchloride-based elastomers, polyolefin-basedelastomers, polyurethane-based elastomers, polyester-based elastomers,polyamide-based elastomers, polybutadiene-based elastomers, and thelike.

And, as the filler which can be included in the resin composition, afiber type, a bead type, a flake type, or a powder type of organic orinorganic filler may be used, as the specific example of the same, theremay be various reinforcements/fillers such as glass fiber, carbon fiber,boron fiber, glass bead, glass flake, talc, calcium carbonate, and thelike. Among the fillers, glass fiber or carbon fiber may berepresentatively used, and the surface of the glass fiber and the likemay be treated or untreated with a silane coupling agent and the like.However, when the surface is treated with the silane coupling agent, thecohesive force or the compatibility of the filler and the polyarylenesulfide may be improved more.

Since the polyarylene sulfide included in the resin composition of oneembodiment shows excellent compatibility with such various polymermaterials or fillers, the resin composition of one embodiment can showexcellent synergistic effect caused by mixing (for example, compounding)with various other polymer materials or fillers, and can show optimizedproperties suitable to various uses. However, it goes without sayingthat other various polymer materials or reinforcements/fillers, inaddition to the polymer materials or fillers disclosed above, may beincluded with the polyarylene sulfide in the resin composition of oneembodiment, and can show more excellent properties. More particularly,various polymer materials or fillers may be included in the resincomposition of one embodiment for further improving the mechanicalproperties, heat resistance, weather resistance, or formability withoutparticular limitation.

And, the resin composition of one embodiment may include about 5 to 95weight % or about 50 to 90 weight % of the polyarylene sulfide and about5 to 95 weight % or about 10 to 50 weight % of one or more componentsselected from the group consisting of thermoplastic resins,thermoplastic elastomers, and fillers. By including each component inabove content range, the resin composition of one embodiment canoptimize the synergistic effect caused by mixing with other componentswhile maintaining excellent properties unique to the polyarylenesulfide, and can exhibit excellent properties preferably applicable tovarious uses.

Meanwhile, the resin composition of one embodiment may further includean additive and/or a stabilizer in order to improve the mechanicalproperties, heat resistance, weather resistance or formabilitysupplementally. The kind of such additive is not limited particularlybut, for example, an oxidation stabilizer, a photo stabilizer (UVstabilizer and so on), a plasticizer, a lubricant, a nucleating agent,or an impact reinforcement may be used, and 2 or more additives selectedfrom them may be further included therein.

Among the additives, a primary or secondary antioxidant may be used asthe oxidation stabilizer, and for example, a hindered phenol-based, anamine-based, or a phosphorous-based antioxidant may be used. And, thephoto stabilizer may be used when the resin composition of oneembodiment is applied to an exterior material, and particularly, an UVstabilizer may be representatively used, for example, benzotriazole orbenzophenol may be used.

And, the lubricant may be used for improving the formability whenshaping or processing the resin composition of one embodiment, and ahydrocarbon-based lubricant may be representatively used. By using thelubricant, it is possible to prevent friction between the resincomposition and a metallic mold or to secure the releasing property forthe secession from a metallic mold.

And, in the process of forming the resin composition, various nucleatingagents may be used for improving the crystallization rate, and, by this,it is possible to improve the solidification rate of the product duringextrusion or molding process and to reduce the cycle time for preparingthe product.

Meanwhile, the resin composition of one embodiment disclosed aboveincludes the melt-polymerized polyarylene sulfide including carboxylgroup (—COOH) or amine group (—NH₂) bonded to the end groups of the mainchain, and the polyarylene sulfide may be prepared by the methodincluding the steps of: polymerizing a reactant including adiiodoaromatic compound and sulfur element; and adding a compound havingcarboxyl group or amine group thereto while carrying out thepolymerization step. And, the method may further include the step ofadding 0.01 to 30 parts by weight of additional sulfur per 100 parts byweight of sulfur element already included in the reactant, for example,in order to regulate the amount of the disulfide repeating unit includedin the polyarylene sulfide to be a proper range. In addition, the methodmay further include the step of adding a polymerization inhibitor at thefixed point of the melt-polymerization step, and such polymerizationinhibitor may be added step by step, dividedly into 2 times or more.

Hereinafter, the preparation method of such polyarylene sulfide isexplained in more detail.

In the preparation method of the polyarylene sulfide, the compoundhaving carboxyl group or amine group may be added thereto when thedegree of polymerization reaction of the diiodoaromatic compound andsulfur element is progressed about 90% or more, or about 90% or more andless than 100%, (for example, in the latter part of the polymerizationreaction), wherein the degree of polymerization reaction is determinedby the ratio of present viscosity to target viscosity. The degree ofpolymerization reaction can be determined as the ratio of presentviscosity to target viscosity. For this, an objective molecular weightof the polyarylene sulfide and a target viscosity corresponding to theobjective molecular weight are set up, and the present viscosityaccording to the degree of polymerization reaction is measured. At thistime, the present viscosity may be differently measured by a methodwell-known to a person skilled in the art in accordance with the scaleof reactor. For example, when the polymerization is carried out in arelatively small polymerization reactor, it may be measured by using aviscometer after taking a sample from the reactor where thepolymerization reaction is progressing. On the other hand, when thereaction is carried out in a huge continuous polymerization reaction,the present viscosity may be measured continuously in real time with aviscometer installed in the reactor itself.

Like this, the melt-polymerized polyarylene sulfide of which carboxylgroup (—COOH) or amine group (—NH₂) is introduced to at least part ofend groups of the main chain can be prepared by adding and reacting thecompound having carboxyl group or amine group in the latter part of thepolymerization reaction of the reactant including the diiodoaromaticcompound and sulfur element. Particularly, since the compound havingcarboxyl group or amine group is added in the latter part of thepolymerization reaction, proper amount of carboxyl group or amine groupcan be introduced to the end groups of the main chain, and thepolyarylene sulfide of one embodiment having not only good compatibilitywith other polymer materials or fillers but also excellent propertiesunique to the polyarylene sulfide can be prepared effectively.

Meanwhile, in the preparation method of the polyarylene sulfide, anarbitrary monomer compound having carboxyl group or amine group may beused as the compound having carboxyl group or amine group. As theexamples of the compound having carboxyl group or amine group,2-iodobenzoic acid, 3-iodobenzoic acid, 4-iodobenzoic acid,2,2′-dithiobenzoic acid, 2-iodoaniline, 3-iodoaniline, 4-iodoaniline,2,2′-dithiodianiline, or 4,4′-dithiodianiline may be used, and variouscompounds having carboxyl group or amine group can be used in addition.

Furthermore, the compound having carboxyl group or amine group may beadded thereto in the amount of about 0.0001 to 5 parts by weight, about0.001 to 3 parts by weight, or about 0.01 to 2 parts by weight, based on100 parts by weight of the diiodoaromatic compound. Proper amount ofcarboxyl group or amine group can be introduced to the end groups of themain chain by adding such amount of the compound having carboxyl groupor amine group, and consequently, the polyarylene sulfide of oneembodiment having not only good compatibility with other polymermaterials or fillers but also excellent properties unique to thepolyarylene sulfide can be prepared effectively.

Furthermore, the polyarylene sulfide is basically prepared by the methodof polymerizing the reactant including diiodoaromatic compounds andsulfur element, and thus it can show superior mechanical properties towhat is prepared by prior Macallum process.

At this time, the diiodoaromatic compound may be one or more compoundsselected from the group consisting of diiodobenzene (DIB),diiodonaphthalene, diiodobiphenyl, diiodobisphenol, anddiiodobenzophenone, but not limited to or by them, diiodoaromaticcompounds that alkyl group or sulfone group is connected to abovecompounds as a substituent or an oxygen or nitrogen atom is included inthe aromatic group may also be used. There are various diiodocompoundisomers of diiodoaromatic compounds depending on the position of iodineatoms, and a compound having iodine at para-position likepara-diiodobenzene (pDIB), 2,6-diiodonaphthalene, or p,p′-diiodobiphenylmay be used more preferably.

And, the form of sulfur element which reacts with the diiodoaromaticcompound is not limited particularly. Generally, sulfur elements existin a cyclooctasulur (S8) form in which 8 atoms are connected at roomtemperature. However, if not such form, any solid type or liquid typesulfur which can be used commercially may be used without particularlimitation.

And, as disclosed above, additional sulfur element may be added duringthe polymerization reaction step in order to regulate the amount of thedisulfide repeating unit included in the polyarylene sulfide, forexample, to regulate the amount to be in the proper range of about 3weight % or less. A person skilled in the art can determine the amountof the added sulfur element by considering proper amount of thedisulfide repeating unit but, for example, the amount may be 0.01 to 30parts by weight per 100 parts by weight of sulfur element included inthe initial reactant. The additional sulfur element may be added whenthe polymerization reaction is progressed about 50 to 99%, for example,and it may be added apart from or in company with the compound havingcarboxyl group or amine group disclose above.

Meanwhile, the reactant for preparing the polarylene sulfide may furtherinclude a polymerization initiator, a stabilizer, or a mixture thereofin addition to the diiodoaromatic compound and sulfur element, and oneor more initiator selected from the group consisting of1,3-diiodo-4-nitrobenzene, mercaptobenzothiazole,2,2′-dithiobenzothiazole, cyclohexylbenzothiazole sulfenamide, andbutylbenzothiazole sulfonamide may be used as the polymerizationinitiator, for example, but it is not limited to or by them.

And, common stabilizer for polymerization reaction or resins may be usedas the stabilizer unlimitedly.

Meanwhile, during the polymerization reaction, a polymerizationinhibitor may be added thereto at the time when the polymerization issomewhat progressed. At this time, any polymerization inhibitor whichcan terminate the polymerization by eliminating iodine group included inthe polymerized polymer can be used without particular limitation.Specifically, one or more compounds selected from the group consistingof diphenyl suldife, diphenyl ether, diphenyl, benzophenone,dibenzothiazole disulfide, monoiodoaryl compound, benzothiazoles,benzotriazoles, benzothiazolesulfenamides, thiurams, dithiocarbamates,and diphenyl disulfide may be used.

More preferably, the polymerization inhibitor may be one or morecompounds selected from the group consisting of iodobiphenyl,iodophenol, iodoaniline, iodobenzophenone, 2-mercaptobenzothiazole,2,2′-dithiobisbenzothiazole, 2,2′-dithiobisbenzotriazole,N-cyclohexylbenzothiazole-2-sulfenamide, 2-morpholinothiobenzothiazole,N,N-dicyclohexylbenzothiazole-2-sulfenamide, tetramethylthiurammonosulfide, tetramethylthiuram disulfide, zinc dimethyldithiocarbamate,zinc diethyldithiocarbamate, and diphenyl disulfide may be used.

Meanwhile, the time of adding the polymerization inhibitor may bedetermined by considering the molecular weight of the polyarylenesulfide to be polymerized finally. For example, the inhibitor may beadded at the time of that about 70 to 100 wt % of the diiodoaromaticcompound included in the initial reactant are reacted and exhausted.

And, the polymerization inhibitor may be added step by step, dividedlyinto 2 times or more, after adding the polymerization inhibitor atfirst. For example, if the amount of the polymerization inhibitor to beused is determined, it is divided into 2 or more doses, for example, 2to 10 doses or 3 to 7 doses, and the inhibitor may be dividedly addedthereto step by step at intervals of about 5 to 30 mins and the rest ofthe polymerization is carried out. By the stepwise insertion of thepolymerization inhibitor, as disclosed above, the linearity of thepolyarylene sulfide polymer chain can be improved and thus it ispossible to obtain excellent compatibility with other polymer materialsor fillers. As the result, the polyarylene sulfide which can becompounded with various materials and can realize optimized propertiessuitable to various uses can be obtained.

And, the polymerization reaction may be carried out in any conditionwhich can initiate the polymerization of the reactant including thediiodoaromatic compound and sulfur element. For example, thepolymerization reaction may be carried out in a temperature-rising andpressure-reducing reaction condition. At this time, the condition may becarried out for about 1 to 30 hrs while varying the temperature andpressure condition from the initial reaction condition of about 180 to250° C. and about 50 to 450 torr to the final reaction condition ofabout 270 to 350° C. and about 0.001 to 20 torr. For more concreteexample, the polymerization reaction may be carried out with the finalreaction condition of about 280 to 300° C. and 0.1 to 0.5 torr.

Meanwhile, the preparation method of the polyarylene sulfide disclosedabove may further include the step of melt-compounding the reactantincluding the diiodoaromatic compound and sulfur element before thepolymerization reaction. The condition of the melt-compounding is notlimited as long as whole reactant is melted and compounded, and forexample, the process may be carried out at the temperature of about 130°C. to 200° C., or about 160° C. to 190° C.

Like this, by carrying out the melt-compounding step before thepolymerization reaction, it is possible to carry out succeedingpolymerization reaction more easily.

Furthermore, in the preparation method of the polyarylene sulfidedisclosed above, the polymerization reaction may be carried out in thepresence of a nitrobenzene-based catalyst. And, when themelt-compounding step is carried out before the polymerization reactionas disclosed above, the catalyst may be added in the melt-compoundingstep. As the nitrobenzene-based catalyst, 1,3-diiodo-4-nitrobenzene, or1-iodo-4-nitrobenzene may be used but it is not limited to or by them.

The melt-polymerized polyarylene sulfide having carboxyl group or aminegroup at the end groups of the main chain can be obtained by thepreparation method disclosed above, and the polyarylene sulfide showsexcellent compatibility with other polymer materials or fillers.Therefore, the resin composition of one embodiment can be obtained byusing the same.

Furthermore, according to another embodiment of the invention, a formedarticle including the polyarylene sulfide resin composition of oneembodiment disclosed above, and the preparation method thereof areprovided. The formed article may be prepared by the method including thestep of extruding the resin composition of one embodiment disclosedabove.

Hereinafter, such formed article and the preparation method areexplained in more detail. However, additional explanation for the kindand the content of the components which can be included in the formedarticle is skipped here because they are already explained about theresin composition of one embodiment.

The formed article of another embodiment includes the melt-polymerizedpolyarylene sulfide having carboxyl group or amine group, one or morecomponents selected from the group consisting of thermoplastic resins,thermoplastic elastomers, and fillers, and selective other additives andit may be prepared by extruding the resin composition of one embodimentprepared by mixing the components.

Such formed article may include about 5 to 95 weight % or about 50 to 90weight % of the polyarylene sulfide and about 5 to 95 weight % or about10 to 50 weight % of one or more components selected from the groupconsisting of thermoplastic resins, thermoplastic elastomers, andfillers, and it may further include about 2 parts by weight, for exampleabout 0.1 to 2 parts by weight, of other additive, per 100 parts byweight of the sum of above two components. For example, the additivesuch as an oxidation stabilizer or a lubricant may be included in theamount of about 0.1 to 1 parts by weight, and the additive such as ahardener may be included in the amount of about 0.1 to 2 parts byweight. The formed article can show excellent properties preferablyapplicable to various uses by satisfying such content range.

Furthermore, when preparing the formed article by mixing and extrudingthe resin composition including the components, a twin screw extruder,for example, may be used, and the aspect ratio (L/D) of such twin screwextruder may be around 30 to 50.

According to one example, the additives included in a small quantity maybe mixed with the polyarylene sulfide in advance by using a mixer suchas a super mixer, and the primary composition mixed beforehand may befed into the twin screw extruder through the main feeder. And, otherpolymer material such as a thermoplastic resin or a thermoplasticelastomer or a filler may be fed separately through the side feederpositioned at the side of the extruder. At this time, the side feedingposition may be the point of about ⅓ to ½ of the whole barrel of theextruder from the outlet. By this, it is possible to prevent the fillerand the like from being broken by the rotation and friction generated bythe screw in the extruder.

The formed article of another embodiment may be obtained by extrudingthe resin composition of one embodiment, after mixing each component ofthe same like this.

The formed article of another embodiment may be various shapes of film,sheet, fiber, and the like. And, the formed article may be an injectionmolded article, an extruded article, or a blown article. In theinjection molding process, the mold temperature may be about 50° C. ormore, about 60° C. or more, or about 80° C. or more in the aspect ofcrystallization, and the temperature may be about 190° C. or less, about170° C. or less, or about 160° C. or less in the aspect of deformationof specimen.

And, if the formed article is a film or a sheet, it may be made into anundrawn, a uniaxially drawn, or a biaxially drawn film or sheet. If itis a fiber, it may be made into an undrawn, a drawn, or an ultradrawnfiber, and it may be used to a fabric, a knit, a nonwoven (spunbond,meltblown, or staple), a rope, or a net.

Such formed articles may be used to electric & electronic parts such ascomputer parts, architectural elements, car parts, machine parts, dailynecessities, coating parts to which chemical materials contact,industrial chemical resistant fiber, and the like.

In the present invention, further details besides the disclosure abovemay be added and subtracted with necessity, and they are not limitedparticularly in the present invention.

Effects of the Invention

The present invention can provides a resin composition including, amelt-polymerized polyarylene sulfide including carboxyl group or aminegroup at the ends of the main chain and showing not only excellentprocessability but also good compatibility with other polymer materialsand/or reinforcements/fillers in company with other polymer material ora filler.

Such resin composition can exhibit excellent properties optimized tovarious uses and excellent properties unique to the polyarylene sulfide.It seems because the compatibility of each component of the resincomposition is increased and the properties of each component can show asynergistic effect.

Therefore, such resin composition can be applied to various uses, andcan exhibit excellent properties and effects.

DETAILED DESCRIPTION OF THE EMBODIMENT

Hereinafter, preferable examples are presented for understanding thepresent invention. However, the following examples are only forillustrating the present invention and the present invention is notlimited to or by them.

Example 1 Synthesis of Polyarylene Sulfide Including Carboxyl Group orAmine Group at the End of the Main Chain

After completely melting and mixing the reactant including 5,130 g ofp-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of1,3-diiodo-4-nitrobenzene as a reaction initiator in a 5 L reactorequipped with a thermocouple capable of measuring the inside temperatureof the reactor and a vacuum line for nitrogen purging and vacuumizing byheating the same to 180° C., the polymerization reaction was proceededby carrying out temperature-rising and pressure reducing step by stepfrom the initial reaction condition of 220° C. and 350 torr to the finalreaction temperature of 300° C. and the pressure of 1 torr or less. Whenthe polymerization reaction was proceeded 80% (the proceeding degree ofthe polymerization reaction was identified by the relative viscosityratio [(present viscosity/target viscosity)*100%], and the presentviscosity was measured with a viscometer after taking a sample from thereactor where the polymerization reaction was progressing), 25 g of2,2′-dithiobisbenzothiazole was added thereto as a polymerizationinhibitor and the reaction was carried out for 1 hr. And then, sulfurwas added thereto 3 times, 0.2 g at a time, at intervals of 1 hour inorder to control the content of the disulfide. Subsequently, afteradding 51 g of 4-iodobenzoic acid thereto when the reaction wasproceeded 90% and progressing the reaction under nitrogen circumstancefor 10 mins, the reaction was further progressed with slowly vacuumizingto 0.5 torr or less for 1 hr, and terminated. By this, the polyarylenesulfide resin having carboxyl group or amine group at the end of themain chain was synthesized. The final resin obtained by the reaction wasprepared into pellets by using a small strand cutter.

The polyarylene sulfide resin of Example 1 was analyzed by FT-IRspectroscopy. At this time, the carboxyl group peak was recognized atabout 1600 to 1800 cm⁻¹ in the spectrum. It was also recognized that therelative height intensity of the peak at about 1600 to 1800 cm⁻¹ wasabout 3.4% when the height intensity of the ring stretch peak shown atabout 1400 to 1600 cm⁻¹ was assumed as 100%.

Example 2 Synthesis of Polyarylene Sulfide Including Carboxyl Group orAmine Group at the End of the Main Chain

After completely melting and mixing the reactant including 5,130 g ofp-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of1,3-diiodo-4-nitrobenzene as a reaction initiator in a 5 L reactorequipped with a thermocouple capable of measuring the inside temperatureof the reactor and a vacuum line for nitrogen purging and vacuumizing byheating the same to 180° C., the polymerization reaction was proceededby carrying out temperature-rising and pressure reducing step by stepfrom the initial reaction condition of 220° C. and 350 torr to the finalreaction temperature of 300° C. and the pressure of 1 torr or less. Whenthe polymerization reaction was proceeded 80% (the proceeding degree ofthe polymerization reaction was identified by the relative viscosityratio [(present viscosity/target viscosity)*100%], and the presentviscosity was measured with a viscometer after taking a sample from thereactor where the polymerization reaction was progressing), 25 g of2,2′-dithiobisbenzothiazole was added thereto as a polymerizationinhibitor and the reaction was carried out for 1 hr. And then, sulfurwas added thereto 3 times, 0.2 g at a time, at intervals of 1 hour inorder to control the content of the disulfide. Subsequently, afteradding 51 g of 4-iodoaniline thereto when the reaction was proceeded 90%and progressing the reaction under nitrogen circumstance for 10 mins,the reaction was further progressed with slowly vacuumizing to 0.5 torror less for 1 hr, and terminated. By this, the polyarylene sulfide resinhaving carboxyl group or amine group at the end of the main chain wassynthesized. The final resin obtained by the reaction was prepared intopellets by using a small strand cutter.

The polyarylene sulfide resin of Example 2 was analyzed by FT-IRspectroscopy. At this time, the amine group peak was recognized at about3300 to 3500 cm⁻¹ in the spectrum. It was also recognized that therelative height intensity of the peak at about 3300 to 3500 cm⁻¹ wasabout 1.4% when the height intensity of the ring stretch peak shown atabout 1400 to 1600 cm⁻¹ was assumed as 100%.

Example 3 Synthesis of Polyarylene Sulfide Including Carboxyl Group orAmine Group at the End of the Main Chain

After completely melting and mixing the reactant including 5,130 g ofp-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of1,3-diiodo-4-nitrobenzene as a reaction initiator in a 5 L reactorequipped with a thermocouple capable of measuring the inside temperatureof the reactor and a vacuum line for nitrogen purging and vacuumizing byheating the same to 180° C., the polymerization reaction was proceededby carrying out temperature-rising and pressure reducing step by stepfrom the initial reaction condition of 220° C. and 350 torr to the finalreaction temperature of 300° C. and the pressure of 1 torr or less. Whenthe polymerization reaction was proceeded 80% (the proceeding degree ofthe polymerization reaction was identified by the relative viscosityratio [(present viscosity/target viscosity)*100%], and the presentviscosity was measured with a viscometer after taking a sample from thereactor where the polymerization reaction was progressing), 25 g of2,2′-dithiobisbenzothiazole was added thereto as a polymerizationinhibitor and the reaction was carried out for 1 hr. And then, sulfurwas added thereto 3 times, 0.2 g at a time, at intervals of 1 hour inorder to control the content of the disulfide. Subsequently, afteradding 25 g of 4-iodobenzoic acid thereto when the reaction wasproceeded 90% and progressing the reaction under nitrogen circumstancefor 10 mins, the reaction was further progressed with slowly vacuumizingto 0.5 torr or less for 1 hr, and terminated. By this, the polyarylenesulfide resin having carboxyl group or amine group at the end of themain chain was synthesized. The final resin obtained by the reaction wasprepared into pellets by using a small strand cutter.

The polyarylene sulfide resin of Example 3 was analyzed by FT-IRspectroscopy. At this time, the carboxyl group peak was recognized atabout 1600 to 1800 cm⁻¹ in the spectrum. It was also recognized that therelative height intensity of the peak at about 1600 to 1800 cm⁻¹ wasabout 2.1% when the height intensity of the ring stretch peak shown atabout 1400 to 1600 cm⁻¹ was assumed as 100%.

Example 4 Synthesis of Polyarylene Sulfide Including Carboxyl Group orAmine Group at the End of the Main Chain

After completely melting and mixing the reactant including 5,130 g ofp-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of1,3-diiodo-4-nitrobenzene as a reaction initiator in a 5 L reactorequipped with a thermocouple capable of measuring the inside temperatureof the reactor and a vacuum line for nitrogen purging and vacuumizing byheating the same to 180° C., the polymerization reaction was proceededby carrying out temperature-rising and pressure reducing step by stepfrom the initial reaction condition of 220° C. and 350 torr to the finalreaction temperature of 300° C. and the pressure of 1 torr or less. Whenthe polymerization reaction was proceeded 80% (the proceeding degree ofthe polymerization reaction was identified by the relative viscosityratio [(present viscosity/target viscosity)*100%], and the presentviscosity was measured with a viscometer after taking a sample from thereactor where the polymerization reaction was progressing), 25 g of2,2′-dithiobisbenzothiazole was added thereto as a polymerizationinhibitor and the reaction was carried out for 1 hr. And then, sulfurwas added thereto 3 times, 0.2 g at a time, at intervals of 1 hour inorder to control the content of the disulfide. Subsequently, afteradding 25 g of 4-iodoaniline thereto when the reaction was proceeded 90%and progressing the reaction under nitrogen circumstance for 10 mins,the reaction was further progressed with slowly vacuumizing to 0.5 torror less for 1 hr, and terminated. By this, the polyarylene sulfide resinhaving carboxyl group or amine group at the end of the main chain wassynthesized. The final resin obtained by the reaction was prepared intopellets by using a small strand cutter.

The polyarylene sulfide resin of Example 4 was analyzed by FT-IRspectroscopy. At this time, the amine group peak was recognized at about3300 to 3500 cm⁻¹ in the spectrum. It was also recognized that therelative height intensity of the peak at about 3300 to 3500 cm⁻¹ wasabout 1.1% when the height intensity of the ring stretch peak shown atabout 1400 to 1600 cm⁻¹ was assumed as 100%.

Example 5 Synthesis of Polyarylene Sulfide Including Carboxyl Group orAmine Group at the End of the Main Chain

After completely melting and mixing the reactant including 5,130 g ofp-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of1,3-diiodo-4-nitrobenzene as a reaction initiator in a 5 L reactorequipped with a thermocouple capable of measuring the inside temperatureof the reactor and a vacuum line for nitrogen purging and vacuumizing byheating the same to 180° C., the polymerization reaction was proceededby carrying out temperature-rising and pressure reducing step by stepfrom the initial reaction condition of 220° C. and 350 torr to the finalreaction temperature of 300° C. and the pressure of 1 torr or less. Whenthe polymerization reaction was proceeded 80% (the proceeding degree ofthe polymerization reaction was identified by the relative viscosityratio [(present viscosity/target viscosity)*100%], and the presentviscosity was measured with a viscometer after taking a sample from thereactor where the polymerization reaction was progressing), 25 g of2,2′-dithiobisbenzothiazole was added thereto as a polymerizationinhibitor and the reaction was carried out for 1 hr. And then, sulfurwas added thereto 3 times, 0.2 g at a time, at intervals of 1 hour inorder to control the content of the disulfide. Subsequently, afteradding 51 g of 2,2′-dithiodibenzoic acid thereto when the reaction wasproceeded 90% and progressing the reaction under nitrogen circumstancefor 10 mins, the reaction was further progressed with slowly vacuumizingto 0.5 torr or less for 1 hr, and terminated. By this, the polyarylenesulfide resin having carboxyl group or amine group at the end of themain chain was synthesized. The final resin obtained by the reaction wasprepared into pellets by using a small strand cutter.

The polyarylene sulfide resin of Example 5 was analyzed by FT-IRspectroscopy. At this time, the carboxyl group peak was recognized atabout 1600 to 1800 cm⁻¹ in the spectrum. It was also recognized that therelative height intensity of the peak at about 1600 to 1800 cm⁻¹ wasabout 3.2% when the height intensity of the ring stretch peak shown atabout 1400 to 1600 cm⁻¹ was assumed as 100%.

Example 6 Synthesis of Polyarylene Sulfide Including Carboxyl Group orAmine Group at the End of the Main Chain

After completely melting and mixing the reactant including 5,130 g ofp-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of1,3-diiodo-4-nitrobenzene as a reaction initiator in a 5 L reactorequipped with a thermocouple capable of measuring the inside temperatureof the reactor and a vacuum line for nitrogen purging and vacuumizing byheating the same to 180° C., the polymerization reaction was proceededby carrying out temperature-rising and pressure reducing step by stepfrom the initial reaction condition of 220° C. and 350 torr to the finalreaction temperature of 300° C. and the pressure of 1 torr or less. Whenthe polymerization reaction was proceeded 80% (the proceeding degree ofthe polymerization reaction was identified by the relative viscosityratio [(present viscosity/target viscosity)*100%], and the presentviscosity was measured with a viscometer after taking a sample from thereactor where the polymerization reaction was progressing), 25 g of2,2′-dithiobisbenzothiazole was added thereto as a polymerizationinhibitor and the reaction was carried out for 1 hr. And then, sulfurwas added thereto 3 times, 0.2 g at a time, at intervals of 1 hour inorder to control the content of the disulfide. Subsequently, afteradding 51 g of 4,4′-dithiodianiline thereto when the reaction wasproceeded 90% and progressing the reaction under nitrogen circumstancefor 10 mins, the reaction was further progressed with slowly vacuumizingto 0.5 torr or less for 1 hr, and terminated. By this, the polyarylenesulfide resin having carboxyl group or amine group at the end of themain chain was synthesized. The final resin obtained by the reaction wasprepared into pellets by using a small strand cutter.

The polyarylene sulfide resin of Example 6 was analyzed by FT-IRspectroscopy. At this time, the amine group peak was recognized at about3300 to 3500 cm⁻¹ in the spectrum. It was also recognized that therelative height intensity of the peak at about 3300 to 3500 cm⁻¹ wasabout 1.3% when the height intensity of the ring stretch peak shown atabout 1400 to 1600 cm⁻¹ was assumed as 100%.

Example 7 Synthesis of Polyarylene Sulfide Including Carboxyl Group orAmine Group at the End of the Main Chain

After completely melting and mixing the reactant including 5,130 g ofp-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of1,3-diiodo-4-nitrobenzene as a reaction initiator in a 5 L reactorequipped with a thermocouple capable of measuring the inside temperatureof the reactor and a vacuum line for nitrogen purging and vacuumizing byheating the same to 180° C., the polymerization reaction was proceededby carrying out temperature-rising and pressure reducing step by stepfrom the initial reaction condition of 220° C. and 350 torr to the finalreaction temperature of 300° C. and the pressure of 1 torr or less. Whenthe polymerization reaction was proceeded 80% (the proceeding degree ofthe polymerization reaction was identified by the relative viscosityratio [(present viscosity/target viscosity)*100%], and the presentviscosity was measured with a viscometer after taking a sample from thereactor where the polymerization reaction was progressing), 25 g of2,2′-dithiobisbenzothiazole was added thereto as a polymerizationinhibitor and the reaction was carried out for 1 hr. And then, sulfurwas added thereto 3 times, 0.2 g at a time, at intervals of 1 hour inorder to control the content of the disulfide. Subsequently, afteradding 25 g of 2,2′-dithiodibenzoic acid thereto when the reaction wasproceeded 90% and progressing the reaction under nitrogen circumstancefor 10 mins, the reaction was further progressed with slowly vacuumizingto 0.5 torr or less for 1 hr, and terminated. By this, the polyarylenesulfide resin having carboxyl group or amine group at the end of themain chain was synthesized. The final resin obtained by the reaction wasprepared into pellets by using a small strand cutter.

The polyarylene sulfide resin of Example 7 was analyzed by FT-IRspectroscopy. At this time, the carboxyl group peak was recognized atabout 1600 to 1800 cm⁻¹ in the spectrum. It was also recognized that therelative height intensity of the peak at about 1600 to 1800 cm⁻¹ wasabout 1.9% when the height intensity of the ring stretch peak shown atabout 1400 to 1600 cm⁻¹ was assumed as 100%.

Example 8 Synthesis of Polyarylene Sulfide Including Carboxyl Group orAmine Group at the End of the Main Chain

After completely melting and mixing the reactant including 5,130 g ofp-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of1,3-diiodo-4-nitrobenzene as a reaction initiator in a 5 L reactorequipped with a thermocouple capable of measuring the inside temperatureof the reactor and a vacuum line for nitrogen purging and vacuumizing byheating the same to 180° C., the polymerization reaction was proceededby carrying out temperature-rising and pressure reducing step by stepfrom the initial reaction condition of 220° C. and 350 torr to the finalreaction temperature of 300° C. and the pressure of 1 torr or less. Whenthe polymerization reaction was proceeded 80% (the proceeding degree ofthe polymerization reaction was identified by the relative viscosityratio [(present viscosity/target viscosity)*100%], and the presentviscosity was measured with a viscometer after taking a sample from thereactor where the polymerization reaction was progressing), 25 g of2,2′-dithiobisbenzothiazole was added thereto as a polymerizationinhibitor and the reaction was carried out for 1 hr. And then, sulfurwas added thereto 3 times, 0.2 g at a time, at intervals of 1 hour inorder to control the content of the disulfide. Subsequently, afteradding 25 g of 4,4′-dithiodianiline thereto when the reaction wasproceeded 90% and progressing the reaction under nitrogen circumstancefor 10 mins, the reaction was further progressed with slowly vacuumizingto 0.5 torr or less for 1 hr, and terminated. By this, the polyarylenesulfide resin having carboxyl group or amine group at the end of themain chain was synthesized. The final resin obtained by the reaction wasprepared into pellets by using a small strand cutter.

The polyarylene sulfide resin of Example 8 was analyzed by FT-IRspectroscopy. At this time, the amine group peak was recognized at about3300 to 3500 cm⁻¹ in the spectrum. It was also recognized that therelative height intensity of the peak at about 3300 to 3500 cm⁻¹ wasabout 1.0% when the height intensity of the ring stretch peak shown atabout 1400 to 1600 cm⁻¹ was assumed as 100%.

Example 9 Synthesis of Polyarylene Sulfide Including Carboxyl Group orAmine Group at the End of the Main Chain

After completely melting and mixing the reactant including 5,130 g ofp-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of1,3-diiodo-4-nitrobenzene as a reaction initiator in a 5 L reactorequipped with a thermocouple capable of measuring the inside temperatureof the reactor and a vacuum line for nitrogen purging and vacuumizing byheating the same to 180° C., the polymerization reaction was proceededby carrying out temperature-rising and pressure reducing step by stepfrom the initial reaction condition of 220° C. and 350 torr to the finalreaction temperature of 300° C. and the pressure of 1 torr or less. Whenthe polymerization reaction was proceeded 80% (the proceeding degree ofthe polymerization reaction was identified by the relative viscosityratio [(present viscosity/target viscosity)*100%], and the presentviscosity was measured with a viscometer after taking a sample from thereactor where the polymerization reaction was progressing), 25 g of2,2′-dithiobisbenzothiazole was added thereto step by step, 5 g at atime, at intervals of 10 mins as a polymerization inhibitor and thereaction was carried out for 1 hr after the last inhibitor was added.And then, sulfur was added thereto 3 times, 0.2 g at a time, atintervals of 1 hour in order to control the content of the disulfide.Subsequently, after adding 25 g of 4-iodobenzoic acid thereto when thereaction was proceeded 90% and progressing the reaction under nitrogencircumstance for 10 mins, the reaction was further progressed withslowly vacuumizing to 0.5 torr or less for 1 hr, and terminated. Bythis, the polyarylene sulfide resin having carboxyl group or amine groupat the end of the main chain was synthesized. The final resin obtainedby the reaction was prepared into pellets by using a small strandcutter.

The polyarylene sulfide resin of Example 9 was analyzed by FT-IRspectroscopy. At this time, the carboxyl group peak was recognized atabout 1600 to 1800 cm⁻¹ in the spectrum. It was also recognized that therelative height intensity of the peak at about 1600 to 1800 cm⁻¹ wasabout 2.2% when the height intensity of the ring stretch peak shown atabout 1400 to 1600 cm⁻¹ was assumed as 100%.

Example 10 Synthesis of Polyarylene Sulfide Including Carboxyl Group orAmine Group at the End of the Main Chain

After completely melting and mixing the reactant including 5,130 g ofp-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of1,3-diiodo-4-nitrobenzene as a reaction initiator in a 5 L reactorequipped with a thermocouple capable of measuring the inside temperatureof the reactor and a vacuum line for nitrogen purging and vacuumizing byheating the same to 180° C., the polymerization reaction was proceededby carrying out temperature-rising and pressure reducing step by stepfrom the initial reaction condition of 220° C. and 350 torr to the finalreaction temperature of 300° C. and the pressure of 1 torr or less. Whenthe polymerization reaction was proceeded 80% (the proceeding degree ofthe polymerization reaction was identified by the relative viscosityratio [(present viscosity/target viscosity)*100%], and the presentviscosity was measured with a viscometer after taking a sample from thereactor where the polymerization reaction was progressing), 25 g of2,2′-dithiobisbenzothiazole was added thereto step by step, 5 g at atime, at intervals of 10 mins as a polymerization inhibitor and thereaction was carried out for 1 hr after the last inhibitor was added.And then, sulfur was added thereto 3 times, 0.2 g at a time, atintervals of 1 hour in order to control the content of the disulfide.Subsequently, after adding 25 g of 4-iodoaniline thereto when thereaction was proceeded 90% and progressing the reaction under nitrogencircumstance for 10 mins, the reaction was further progressed withslowly vacuumizing to 0.5 torr or less for 1 hr, and terminated. Bythis, the polyarylene sulfide resin having carboxyl group or amine groupat the end of the main chain was synthesized. The final resin obtainedby the reaction was prepared into pellets by using a small strandcutter.

The polyarylene sulfide resin of Example 10 was analyzed by FT-IRspectroscopy. At this time, the amine group peak was recognized at about3300 to 3500 cm⁻¹ in the spectrum. It was also recognized that therelative height intensity of the peak at about 3300 to 3500 cm⁻¹ wasabout 1.3% when the height intensity of the ring stretch peak shown atabout 1400 to 1600 cm⁻¹ was assumed as 100%.

Comparative Example 1

The polyarylene sulfide (MV: 2,000 poise, Tm: 282° C.; Celanese) made byMacallum process was prepared.

Comparative Example 2

The polyarylene sulfide (MV: 2,300 poise, Tm: 281° C.; Deyange) made byMacallum process by other company than Comparative Example 1 wasprepared.

Comparative Example 3

Product name Z200 of DIC Co., Ltd. in which the polyarylene sulfide madeby Macallum process was compounded with an elastomer was used asComparative Example 3.

Experimental Example 1 Evaluation on Basic Properties of PolyaryleneSulfide

The properties of polyarylene sulfides of Examples 1 to 10 andComparative Examples 1 and 2 were evaluated by the following methods:

Melting Temperature (Tm)

By using a differential scanning calorimeter (DSC), after elevating thetemperature of the specimen from 30° C. to 320° C. with a scanning speedof 10° C./min and cooling to 30° C., the melting temperature wasmeasured while elevating the temperature from 30° C. to 320° C. againwith a scanning speed of 10° C./min.

Number Average Molecular Weight (Mn) and Polydispersity Index (PDI)

After dissolving the polyarylene sulfide in 1-chloronaphthalene at 250°C. for 25 minutes with stirring so as to be 0.4 wt % solution, thepolyarylene sulfide was divided in order in the column of a hightemperature gel permeation chromatography (GPC) system (210° C.) byflowing the solution with the flow rate of 1 mL/min, and the intensitycorresponding to the molecular weight of the divided polyarylene sulfidewas measure by using a RI detector. After making a calibration line witha standard specimen (polystyrene) of which the molecular weight wasknown, the relative number average molecular weight (Mn) andpolydispersity index (PDI) of the measure sample was calculated.

Melt Viscosity (Poise)

The melt viscosity (hereinafter, ‘M.V.’) was measured at 300° C. byusing a rotating disk viscometer. In frequency sweep measuring method,angular frequency was measured from 0.6 to 500 rad/s, and the viscosityat 1.84 rad/s was defined as the melt viscosity (M.V.).

Measurement on Flowability of Polymer

A spiral test which has been generally used for measuring theflowability of polymerized polymer was used. For the following test,every polymerized specimen was cut into pellets having the diameter of1˜2 mm and the length of 2˜4 mm during the polymer came out of thepolymerization reactor. At this time, the maximum injection pressure inthe injection machine, the injection charge, the ejection rate, thepressure of injection, and the holding pressure were uniformlyregulated, and the injection temperature (based on barrel) was fixed to320° C. After the spiral test, the final length of the formed articleseparated from the mold was measured, and the results are listed inTable 1.

Measurement on Flashes Formed During the Preparation of Formed Article

After spiral test was carried out by using the polymers of ComparativeExamples and Examples, except the main shaped body corresponding to themold which was used to the spiral test, the thin parts held between thefront part and the back part of the mold were cut and weighed asflashes.

The properties measured like above are listed in the following Table 1:

TABLE 1 Number Amount of Melting Average Polydispersity Melt Flashtemperature Molecular Index Viscosity Flowability GenerationClassification (° C.) Weight (PDI) (Poise) (cm) (g) Example 1 278.617,667 2.9 2,940 48 0.01 Example 2 278.3 17,614 2.9 2,200 58 0.15Example 3 278.8 17,435 2.8 2,830 50 0.04 Example 4 278.6 17,224 2.82,770 52 0.08 Example 5 277.5 17,338 2.9 2,350 58 0.12 Example 6 277.717,152 2.9 2,930 49 0.01 Example 7 278.3 17,531 2.8 2,470 57 0.15Example 8 278.7 17,582 2.8 2,530 55 0.10 Example 9 279.1 17,884 2.82,450 58 0.08 Example 10 279.0 17,912 2.8 2,360 59 0.12 Comparative282.0 15,237 3.1 2000 62 0.54 Example 1 Comparative 281.0 10,543 3.32300 57 0.42 Example 2

Referring to Table 1, it is recognized that the polyarylene sulfides ofExamples including the polyarylene disulfide repeating unit formed byadding sulfur during the preparation process show excellentprocessability when forming an article requiring high degree ofprecision because of their optimized flowability and small amount offlash generation. On the contrary, it is recognized that the polyarylenesulfides of Comparative Examples 1 and 2 show inferior processability tothe polyarylene sulfides of Examples because of relatively large amountof flash generation.

Experimental Example 2 Evaluation on Mechanical Properties ofPolyarylene Sulfide

The mechanical properties of polyarylene sulfides of Examples 1 to 10and Comparative Examples 1 and 2 were evaluated by the followingmethods:

Tensile Strength and Elongation

The tensile strength and the elongation of the polyarylene sulfidespecimens prepared according to Examples 1 to 10 and ComparativeExamples 1 and 2 were measured according to ASTM D 638 method.

Flexural Strength

The flexural strength of the polyarylene sulfide specimens preparedaccording to Examples 1 to 10 and Comparative Examples 1 and 2 weremeasured according to ASTM D 790 method.

Impact Strength (Izod)

The impact strength of the polyarylene sulfide specimens preparedaccording to Examples 1 to 10 and Comparative Examples 1 and 2 wasmeasured according to ASTM D 256 method.

The mechanical properties measured according to above methods are listedin the following Table 2:

TABLE 2 Tensile Flexural Impact Strength Elongation Strength StrengthClassification (kgf/cm²) (%) (kgf/cm²) (J/m, Notched) Example 1 612 2.21,430 17 Example 2 602 1.2 1,422 20 Example 3 622 2.1 1,433 18 Example 4614 1.3 1,442 17 Example 5 628 2.2 1,455 18 Example 6 605 1.2 1,428 17Example 7 611 2.3 1,435 17 Example 8 618 1.3 1,447 19 Example 9 630 2.41,475 22 Example 10 625 1.5 1,465 20 Comparative 650 3.4 1,490 27Example 1 Comparative 647 2.8 1,475 25 Example 2

The specimens were prepared by compounding the polyarylene sulfide ofExamples 1 to 8 and Comparative Example 1 with other componentsaccording to the following methods:

Compounding of Polyarylene Sulfide and Glass Fiber (GF)

After drying the polymerized resin, the compounding was carried out witha small twin-screw extruder under the condition of the extrusion dietemperature of 300° C. and the screw speed of 200 rpm while adding 40parts by weight of glass fiber to 60 parts by weight of the resin.

Compounding of Polyarylene Sulfide and Elastomer

The mixing extrusion was carried out under the condition of theextrusion die temperature of 300° C. and the screw speed of 200 rpmwhile adding 10 parts by weight of Lotader (Grade AX-8840, made byArkema), the elastomer, to 90 parts by weight of the resin.

The mechanical properties of the compounded specimens were evaluated bythe same way as the polyarylene sulfide specimens and are listed in thefollowing Table 3. Furthermore, such mechanical properties are listedtogether in the following Table 3 compared to the commercializedcompounded specimen of Comparative Example 3:

TABLE 3 Tensile Flexural Impact Strength Elongation Strength StrengthClassification (kgf/cm²) (%) (kgf/cm²) (J/m, Notched) Example 1 + 58325.2 1,030 54 Elastomer 10% Example 2 + 1,750 1.8 2,440 85 GF 40%Example 3 + 577 20.5 1,010 48 Elastomer 10% Example 4 + 1,740 1.8 2,40083 GF 40% Example 5 + 564 24.3 1,010 52 Elastomer 10% Example 6 + 1,7701.8 2,480 86 GF 40% Example 7 + 568 18.7 1,005 45 Elastomer 10% Example8 + 1,750 1.8 2,420 82 GF 40% Example 9 + 603 27.5 1,130 60 Elastomer10% Example 10 + 1,840 2.2 2,650 92 GF40% Comparative 660 15.7 940 76Example 3 (Elastomer compounding)

According to Tables 2 and 3, it was recognized that the elongation andthe impact strength were largely increased by compounding thepolyarylene sulfides of Examples 1 to 10 of which carboxyl group oramine group is introduce to the end of the main chain with thethermoplastic elastomer. And, it was recognized that the tensilestrength was largely increased by compounding the polyarylene sulfidesof Examples 1 to 10 with glass fiber. And, it was recognized that theelongation and the impact strength of the polyarylene sulfide of Example9 prepared by adding the polymerization inhibitor step by step werelargely improved by compounding the same with the thermoplasticelastomer. And, it was recognized that the tensile strength and theimpact strength of the polyarylene sulfide of Example 10 were largelyimproved by compounding the same with the glass fiber. From theimprovement of the properties caused by such compounding, it isrecognized that the polyarylene sulfides of Examples can show excellentcompatibility with various other polymer materials or fillers and thusthe compounded resin composition can show excellent synergistic effect.

On the other hand, it was recognized that the polyarylene sulfides ofComparative Examples were inferior in the compatibility with otherpolymer materials or fillers and the synergistic effects caused bycompounding was not so big.

What is claimed is:
 1. A polyarylene sulfide resin composition,including a polyarylene sulfide including a disulfide repeating unit inthe repeating units of the main chain; and at least one componentselected from the group consisting of a thermoplastic resin, athermoplastic elastomer, and a filler.
 2. The polyarylene sulfide resincomposition according to claim 1, wherein the disulfide repeating unitis included in the amount of 3 weight % or less, based on the wholepolyarylene sulfide.
 3. The polyarylene sulfide resin compositionaccording to claim 1, wherein the polyarylene sulfide is prepared bymelt-polymerizing a reactant including diiodoaromatic compounds andsulfur element while adding the polymerization inhibitor step by step,dividedly into 2 times or more.
 4. The polyarylene sulfide resincomposition according to claim 1, wherein the polyarylene sulfideincludes carboxyl group (—COOH) or amine group (—NH₂) bonded to at leastpart of end groups of the main chain.
 5. The polyarylene sulfide resincomposition according to claim 4, wherein the polyarylene sulfide showsthe peak of 1600 to 1800 cm⁻¹ or 3300 to 3500 cm⁻¹.
 6. The polyarylenesulfide resin composition according to claim 5, wherein the relativeheight intensity of the peak of 1600 to 1800 cm⁻¹ or 3300 to 3500 cm⁻¹is 0.001 to 10%, when the height of the ring stretch peak shown at 1400to 1600 cm⁻¹ is assumed as the intensity of 100%, in the FT-IR spectrumof the polyarylene sulfide.
 7. The polyarylene sulfide resin compositionaccording to claim 1, wherein the thermoplastic resin is one or moreselected from the group consisting of polyvinylalcohol-based resins,vinylchloride-based resins, polyamide-based resins, polyolefin-basedresins, and polyester-based resins.
 8. The polyarylene sulfide resincomposition according to claim 1, wherein the thermoplastic elastomer isone or more selected from the group consisting ofpolyvinylchloride-based elastomers, polyolefin-based elastomers,polyurethane-based elastomers, polyester-based elastomers,polyamide-based elastomers, and polybutadiene-based elastomers.
 9. Thepolyarylene sulfide resin composition according to claim 1, wherein thefiller is a fiber type, a bead type, a flake type, or a powder type oforganic or inorganic filler.
 10. The polyarylene sulfide resincomposition according to claim 1, wherein the filler is one or moreselected from the group consisting of glass fiber, carbon fiber, boronfiber, glass bead, glass flake, talc, and calcium carbonate.
 11. Thepolyarylene sulfide resin composition according to claim 1, wherein thenumber average molecular weight of the polyarylene sulfide is 5,000 to50,000.
 12. The polyarylene sulfide resin composition according to claim1, including 5 to 95 weight % of the polyarylene sulfide and 5 to 95weight % of one or more components selected from the group consisting ofthermoplastic resins, thermoplastic elastomers, and fillers.
 13. Thepolyarylene sulfide resin composition according to claim 1, furtherincluding an oxidation stabilizer, a photo stabilizer, a plasticizer, alubricant, a nucleating agent, and an impact reinforcement.
 14. A methodof preparing a formed article, including the step of extruding the resincomposition of claim
 1. 15. The method according to claim 14, theextrusion is carried out with a twin screw extruder.
 16. A formedarticle, including the polyarylene sulfide resin composition accordingto claim
 1. 17. The formed article according to claim 16, which is aform of film, sheet, or fiber.
 18. The formed article according to claim16, which is used to car interior parts, car exterior parts, electricparts, electronic parts, or industrial materials.
 19. A method ofpreparing a formed article, including the step of extending the resincomposition of claim
 2. 20. A formed article, including the polyarylenesulfide resin composition according to claim 4.